Albert herrmann



STATES PATENT OFFICE.-

ALBERT HEBRMANN,OF HUCHST-ON-THE-MAIN, GERMANY, ASSIGNOR TO THE FARBWERKE, VORMALS MEISTER, LUOIUS & BRUNING, OF SAME PLACE.

COLORING-MATTER.

srncrrrcnrron forming part of Letters 1 mm No. 412,613, dated October 8, 1889.

Application filed January 15, 1889| Serial No. 296,889- (Specimens) Patented in Germany August 18, 1888 in Belgium September 3, 1888,110. 83,115; in France September 5, 1888,11'0. 192,807, and in Italy'8eptember 30, 1888,XLVII, 1'76.

To all whom it may concern.-

Be it known that I, ALBERT HERRMANN, a citizen of the Empire of Germany, residing at Hochst-on-the-Main, in the Empire of Ger- 5 many, have invented certain new and useful Improvements in Coloring-Matters, (the same having been patented in France September 5, 1888, No. 192,807 in Germany AugustlS, 1888, F. 3,757; in Belgium September 3,1888,No.

83,115, and in Italy September 30, 1888, No. 176,V01. 47;) and I do hereby declare the following to be a full, clear, and exact descrip tion of the invention, such as will enable others skilled in the art to which it appertains to I5, make and use the same."

My invention relates to the production of green-blue coloring-matter to be considered as derivative of the metaoxydiamidotriphenyl methane r onogrnnn, ,C H NH Theleuco base of this coloring-matter is pro- 2" 5 duced by condensing metanitrobenzaldehyde with tertiary aromatic amines, (Bemchte der acids excel the various sorts of acid green offered in the trade by their special resistance to the influence of light, and .also by their special fastness in Washing.

I. PRODUOTlION OF METAOXYTETRALKYLDI AMIDOTRIPHENYL METHANE.

A. Conversion of meia-arn'idoteiralkyldiamidotm'phenyl methane into the corresponding metaoocytetralkyldtamrldotmphenyl meth cme by means of nitrous acid'.The following is given as an example of carrying out the conversion: Fifty parts, by weight, of meta-amidotetraethyldiamidotriphenyl methane are dissolved in thirty-five parts, by weight, of hydrochloric acid (of thirty-three per cent.) and five thousand parts, by weight, of water. The solution is cooled down to O centigrade, and while itis kept well stirred there is slowly added a cold solution of 8.9 parts, by weight, of nitrite, (of 96.5 per cent.) The solution of the hydrochlorate of metadiazotetraethyh diamidotriphenyl methane is heated slowly and kept at 60 centigrade for some time, until the liberation of nitrogenhas become rather feeble. It is then boiled until the liberation of nitrogen ceases. To the acid solution is added soda-lye until it shows a slight alkaline reaction. By these means the metaoxy leuco base is precipitated in the form of a crystalline powder. It is filtered oft, boiled with water, and afterward dried. In a similar manner is carried out the production of the other metaoxytetralkyldiamidotriphenyl methanes, (obtained from the meta-amido leuco bases,) which, like the ethyl compound mentioned before, have relatively strong basic qualities via, of metaoxytetramethyldiamidotriphenyl methane, symmetric metaoxydimethyldiethyldiamidotriphenyl methane canon ia mr sna at unsymmetric metaoxydimethyldiethyldiamidotriphenyl methane on on or-iioinjn (n1 2 metaoxytetramethyldiamidodiorthotolylphe nyl methane, and metaoxytetraethyldiamidodiorthotolylphenyl methane.

The process of the production of the metaoxy leuco bases showing slighter basic qualitiessuch as, for example, metaoxydibenzyl diethyldiamidotriphenyl methane V C H NH i ma e ie s)].

are dissolved in thirty parts, by weight, of concentrated sulphuric acid and about four thousand parts, by weight, of water. The solution is cooled down to 0 centigrade, and then there is added slowly a cold solution of 4.7 7 parts, by weight, of nitrite, (of 96.6 per cent.) The decomposition of the diazo compound thus obtained by boiling with water is carried out as described above. Of the metaoxy leuco bases thus formed the greatest part precipitates in crystalline form, and what of it remains in solution is precipitated from the liquid by the addition of sulphate of sodium. The oxy leuco base precipitated forms a crystalline powder, which, in order to free it from the accompanying acid, &c., is boiled with water until it shows neutral reaction. In a similar manner are prepared metaoxydibenzyldimethyldiamidotriphenyl methane, metaoxydimethyldiphenyldiamidotriphenyl methane, and metaoxydiethyldiphenyldiamidotriphenyl methane.

B. Production of metaoxytetralkyldiamidotriphenyl methane by condensing metaoccybenzaldehyde with tertiary aromatic bases. The production of the tetraethyl compound, for example, may be carried out in the following manner: Twenty parts, by weight, of diethylaniline, eight parts, by weight, of con.- centrated sulphuric acid, and nine parts, by weight, of inetaoxybenzaldehyde are heated in a lead-lined boiler furnished with an agitator to 130 centigrade for three to twentyfour hours. The mass resulting is supersaturated with soda-lye, and the excess of diethylaniline expelled by a current of steam. The oxy leuco base remaining is repeatedly boiled with water and afterward dried. In a similar manner are obtained by this process the leuco bases mentioned above, if for the diethylaniline is substituted dimethylaniline, methylet-hylaniline, ethylbenzylaniline, methylbenzylaniline, dimethyl orthotoluidine, diethyl-orthotoluidine, methyl-diphenylamine, or ethyl-diphenylamine.

The metaoxytetralkyldiamidotriphenyh methanes produced according to the processes described are in pure state colorless crystalline compounds; but it is rather difficult to obtain them quite colorless, as by the contact of the atmosphere they become soon colored.

The bases dissolve quite easily in ether,

benzol, and toluol, not so easily in alcohol, and are insoluble in Water. w 1

The oxy compounds do not dissolve in diluted alkalies.

II. PRODUCTION OF THE SULPHONIC ACID OF M E T AOXYTETRAL K YL DIAM I DOTR I PH ENYL METHANE.

The metahydroxylized leuco bases ofthe generic formula CH canon at ordinary temperature until a sample gives with diluted ammonia a clear solution. Now the product of the reaction is poured into water and the solution converted into the calcium salt in well-known manner, The calcium salt is a powder very easily soluble in alcohol and in water. In the same manner is carried out the production of the sulphonio acids, respectively, of their calcium salts of metaoxytetramethyldiamidotriphenyl methane, symmetric metaoxydimethyldiethyldi amidotriphenyl methane, unsymmetric metaoxydimethyldiethyldiamidotriphenyl methane, metaoxytetramethyldiamidodiorthotolylphenyl methane, and metaoxytetraethyldiamidodiorthotolylphenyl methane.

Example No. 2.-Somewhat differentis the process for, the preparation of the sulphonic acids of those leuco bases which in the amido group still contain aromatic residues, (capable of being sulphonated,) such as benzyl or phenyl. The compounds belonging to this class are the following: metaoxydibenzyldiethyldiamidotriphenyl methane, metaoxydibenzyldimethyldiamidotriphenyl methane, metaoxyd i ph enyldiet hyld iamidotri p h enyl methane, and metaoxydiphenyldimethyldiamidotriphenyl methane.

In the following example is described the way in which is carried out the sulphonation of these leuco bases: Thirty parts, by weigh t, of metaoxydibenzyldiethyldiamido1riphenyl methane are dissolved in one hundred and fifty parts, by weight, of fuming sulphuric acid of twenty per cent. 30,. At ordinary temperature is formed a sulphonic acid scarcely soluble in water. Then the solution is heated for several hours to abont 7 0 centigrade, until a sample dissolves easily in water with blue color and gives with diluted ammonia a pure blue solution having the shade of a diluted ammoniacal solution of oxide of poured into water and converted into the calcopper. N ow the product of the reaction is cium saltin manner well known.

III.OXIDATION OF TlzllE LEUOO SULPHONIC ACID.

From the calcium salts of the leuco-sulphonic acids mentioned in II is prepared, by oxidation with superoxides or similar agents in pres- 61106 or the calculated quantity of -mineral acids, the corresponding coloring-matter. For

example, ten parts, by weight, of the calcium salt of .the sulphonic acid prepared from meta oxytetraethyldiamidotriphenylmethane are dissolved in about three hundred parts, by weight, of water. Then there are added the calculated quantities of diluted sulphuric acid and superoxide of lead filtered ofi from the precipitated sulphate of lead, and the blue solution of the coloring-matter is evaporated 'to dryness.

The new coloring-matter is in form of a coppered' powder of metallic luster, dissolving quite easily inwater, giving blue color. The aqueous solution turns green on the addition of an excess of mineral acid. The blue color of the aqueous solution does not disappear on the addition of soda-lye when cold,

, invention.

not even when it is boiledwith a solution of ammonia or soda, and it turns violet only when it is boiled withsoda-lye. This characteristic quality of the new coloring-inatter namely, the great resistance to the action of alkalies-is a great advantage. for technical purposes, and constitutes a great merit of the These compounds dye wool and silk in an acid bath a green'blue shade, and

excel in dyeing an even tint, in which respect the sulphonic acids of indigo are equaled. In consequence of the resistance to alkalies the tints produced are (compared to those produced with indigo carmine very fast in Washing.

IV.CONVERSION OF METAOXYTETRALKYL- DIAMIDOTRIPHENYL GARBINOL INTO THE ACID COLORING-MATTER DESCRIBED IN SUB. III.

The same coloring-matter may be obtained also by sulphonating metaoxytetralkyldi 'in diluted ammonia with blue color.

amidotriphenyl carbinol. This compound is formed by treatment of the leuco bases described in sub. I with superoxides or similar agents, and is a yellow-green coloring-matter, the salts of which excel by their great aptness to crystallize. The sulphates or chlorhydrates of this carbinol,

viz., of metaoxytetramethyldiamidotriphenyl carbinol, metaoxytetraethyldiamidotriphenyl carbin ol, symmetric metaoxydimethyldiethyldiamidotriphenyl carbinol, unsymmetric metaoxydimethyldiethyldiamidotriphenyl carbinol, metaoxytetramethyldiamidodiorthotolylphenyl carbinol, and metaoxytetraethyldi-- amidodiorthotolylphenyl carbinoL-maybe converted by treatment with sulphuric acid into acid coloring-matter identical with the coloring-matter described in III.

The conversion is, for example, carried out in the following way: Tenparts, by Weight, of metaoxytetraethyldiamidotriphenyl carbinol are dissolved in sixty parts, by weight, of monohydrate and the solution heated to 50 to centigrade, until a sample dissolves The product of the reaction is then converted into the calcium or sodium salt in manner wellknown.

"What I claim as new, and desire to secure ALBERT HERRMANN.

Witnesses:

J osnr REVERDY, HEINRICH HAHN. 

